Exchange resins from vinylbenzyl sulfonium resins and method for making same



United States Patent M EXCHANGE RESINS FRQM VHNYLBENZYL SULFO- NIUMRESXNS AND METHOD FOR MAKING SAME Melvin J. Hatch, Midland, Mich,assignor to The Dow Chemical Company, Midland, Micln, a corporation ofDelaware No Drawing. Filed Feb. 16, 1961, Ser. No. 89,647

20 Claims. (Cl. 26i)--2.1)

This application is a continuation-in-part of US. patent applicationSerial No. 771,205, filed November 3, 1958, now abandoned, which inturn, is a continuation-inpart of US patent application Serial No.674,014, filed July 25, 1957, now abandoned.

This invention concerns a method for preparing ion exchange resins andproducts thereof. More particularly, it concerns the preparation ofcation, anion and chelating exchange resins (hereafter exchange resins)by reacting a polymeric vinylbenzylic sulfonium anion exchange resinwith an ionizable reagent to establish a covalent bond therewith to givea substituted resinous vinylbenzylic polymer having ion exchangingmoieties (hereafter exchanging moieties) or moieties which can behydrolyzed or oxidized to give exchanging moieties.

Vinylaryl polymers containing halomethyl groups, such as vinylbenzylchloride or bromide polymers and cop-olymers, and chloromethylated orbromomethylated polymeric styrene, including crosslinkedchloromethylated or bromomethylated styrene copolymers, are not easilyreacted with various nucleophilic reagents, such as the water-solublespecies,

NITQCHZC O ONa, NaSOI-hC O ONa, NH CIHCO Na CHzC OzNa SQ3Na CO2N21POsNai CH2, NH2OR, NH2C-R, N32S203 NI-I OR R I i NaS-CHOOzNaN-(methyD-glucarninc, NflzSOa, 0 H2O OgNtl and the like, wherein R ishydrogen, an alkyl group, an aryl group, a substituted alkyl, or asubstituted aryl group to establish a covalent bond therewith and togive a resinous polymer having one or more exchanging moieties. Thisdifiiculty is due mostly to the hydrophobic nature of the polymer matrixwhich contains halomethyl groups. Mutual solvents which will swell thepolymer matrix and also dissolve such reagents are often not practicalbecause of inefiiciency in promoting the reaction. The same is oftentrue with analogous reagents which can be converted to have exchangingmoieties by a simple hydrolysis or oxidation reaction involving theirsubstituent moieties.

It has now been discovered that polymeric vinylbenzylic sulfonium anionexchange resins can be reacted readily in swollen condition with asolution of a reagent of the type indicated above, often in aqueoussolution, to give an exchange resin or which upon oxidation orhydrolysis can be converted to give an exchange resin. Highly polarsolvents such as water-soluble alcohols and water-insoluii ihdfilfiPatented Jan. 24, 1967 insoluble solvents or diluents dispersed in watercan be.

used.

Although it is generally desirable to have the vinylbenzylic sulfoniumresin in a water-swollen condition for reaction with the nucleophilicreagent, this is not always essential. A polar solvent or the reagentitself often can act as a swelling agent for the vinylbenzylic sulfoniumresin. Whenever the reagent can be absorbed into the sulfonium resin, asby ion exchange absorption, and re main in the resin phase when thesolvent is removed, it is possible to obtain reaction merely by heatingthe dry sulfonium resin which contains the absorbed nucleophilicreagent. Thus, the method of this invention makes it possible to bringthe reagent and the reactive parts of the vinylbenzylic anion exchangeresin in reactive contact.

The polymeric vinylbenzylic sulfonium halide anion exchange resinsadvantageously used in making the exchange resins pursuant to theprocedure of this invention are the reaction products of (a) vinylarylpolymers such as those of styrene, vinyltoluene, vinylxylene,chlorostyrene, dichlorostyrene, vinylnaphthalene, acenaphthene, etc.containing an average of between about 0.25 and 1.5 halomethyl groupsper aromatic nucleus, which are cross-linked, advantageously to theextent of between 0.2 and 20 weight percent, with a conventionalcrosslinking agent, e.g., a dialkenyl crosslinking agent such asdivinylbenzene (DVB), divinyltoluene, divinylxylene, trivinylbenzene,diallyl esters, ethylene glycol dia-crylate and dimethacrylate, etc.;and (b) a sulfide which contains 1 or 2 alkyl groups containing between1 and 4 carbon atoms and/or, correspondingly, 1 or 2 hydroxyalkyl groupscontaining between 2 and 4 carbon atoms, i.e., dimethyl, diethyl,dipropyl, methyl hydroxyethyl, dibutyl sulfide; polymethylene sulfidesand alkyl substituted polymethylene sulfides having 4 to 12 carbonsatoms, from 4 to 8 of which are polymethylenic, the balance being from 1to 4- carbon alkyl groups, etc, pursuant to the procedure of copendingUS, patent application, Serial No. 769,545, filed October 27, 1958, andnow abandoned. The sulfonium anion exchange resin can be reacted in thehalide form, as produced, or it can be converted to other ionic formsbefore reaction, e.g., the sulfate form.

In practice, the exchange resins of this invention are made by reactinga swollen polymeric vinylbenzylic sulfonium anion exchange resin, asindicated above, with a stoichiometric proportion of a nucleophilicreagent to establish a covalent bond with the benzylic carbon atoms ofsaid resin, giving a sulfide by-product and yielding a substitutedvinylbenzylic resin which has exchanging moieties, sometimes at the atomof the reagent which establishes the covalent bond, e.g., with aminereagents, or, alternatively, to yield a substituted vinylbenzylic resinwhich has moieties which can be converted to exchanging moieties by asimple hydrolysis or a simple oxidation reaction, e.g., withmercaptoalkanecarboxylic esters, mercaptoalkyl nitriles, andB-mercaptoalkanols The nucleophilic reagents which can be reacted withsaid sulfonium anion exchanging resins to give different exchangingresins are those which are ionizable and have an exchanging moiety(group) or a moiety which can be transformed to an exchanging moiety bya simple hydrolysis or oxidation reaction, are soluble to the extent ofat least weight percent in water, aliphatic liquid monohydric andpolyhydric alcohols having up to carbon atoms, liquid dihydric alcoholpolymers such as poly (ethylene glycol), poly(propylene glycol) andpolymeric mixtures of ethylene and propylene glycol having up to 10carbon atoms and/or lower monoalkyl ethers of liquid dihydric alcoholpolymers, having up to 10 carbon atoms; which reagents react instoichiometric proportions at 20 to 100 C. with benzyl chloride todisplace at least 5 mole percent of chloride therefrom in 48 hours toform a covalent linkage with the benzylic carbon atom. By ionizable ismeant a reagent which has a measurable ionization in solution. Thesecharacteristics of the nucleophilic reagents used in the method of thisinvention encompass many diverse operable compounds and excludeinoperable compounds. The characterizing data make definite and certainto the art skilled these numerous reagents. By way of example, thesereagents include simple amines and polyamines free from hydrocarbonyland substituted hydrocarbonal groups, e.g., NH3, NH2OH, NH2-'NH2, and(NH NH) CO; metal salts of H 80 H S O HSCN, H 8, H S (n=2, 3 or 4) andHCN; metal salts of activated methylene or methine groups, e.g., of CH(COOR) RCOCH COOR, CH(CH )(COOR) RCOCH SO C H RCOCH NO RCOCHCH NO RCOCHCN, ROCOCH CN, RCOCH COOR, where R is an alkyl group having from 1 to 8carbon atoms; hydrocarbonyl and substituted hydrocarbonyl amines andhydrazines, whether primary, secondary or tertiary, e.g., methylamine,n-amylamine, benzylamine, iso-propylamine, sec.-butylamine, allylamine,n-propylamine, nbutylamine, iso-amylamine, iso-butylamine,2-aminoethanol, 1 amino 2 propanol, histamine, 2-amino-2-methyl-l-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2 methoxyethylamine,n-hexylamine, p-methoxybenzylamine, 3-isopropoxy-n-propylamine,2-ethylhexylamine, tert.-butylmine, 3-amino-1-propanol, n-octylamine,n-dodecylamine, n-decylamine, L-(+)histidine, diethylamine,dimethylamine, dibenzylamine, di-n-propylamine, di-n butylamine,di-iso-amylarnine, 2-2-iminodiethanol, diallylamine, di-n-arnylamine,1-diethylamino-Z-propanol, l-adrenaline, di-sec.-butylamine,di-n-heptylamine, di-nhexylamine, B,fi'-iminodipropionitrile,N-methyltaurine sodium salt, N-methylcyclohexylamine,2-ethylaminoethanol, N-ethyl-n-butylamine, iminodiacetic acid disodiumsalt monohydrate, iminodiacetonitrile, diethyl iminodiacetate,N-methyl-n-butylamine, trimethylamine, triethylamine,2-dimethylaminoethanol, 2-diethylaminoethanol, 3 diethylamino 1propanol, 2,2,2-nitrilotriethanol, tri-iso-amylamine, tri-n-amylamine,Z-di-n-butylaminoethanol, 3-di-n-butylamino-l-propanol,diethylaminoacetonitrile, 1 dimethylamino 2 propanol,fi-dimethylaminopropionitrile, triallylamine, 1 di nbutylamino-2-propanol, hexamethylenetetramine, ethylenediamine, 1,2-propanediamine, triethylenetetramine, diethylenetriamine,N,N-diethylethylenediamine, tetraethylenepentamine, 1,6-hexanediamine,N,N-dimethyl-1, 3-propanediamine, 3,3 -diaminodipropylamine,1,8-pmethanediamine, p-aminobenzoic acid metal salts, aniline,o-anisidine, p-anisidine, l-naphthylamine, 4-aminol-naphthalenesulfonicacid sodium salt, sulfanilic acid sodium salt, 3-amino-p-toluenesulfonicacid metal salts, 1-amino-2-naphthol-4-sulfonic acid metal salts,o-aminophenol, p-aminophenol, 5-amino-2-naphthalenesulfonic acid metalsalts, 2-amino-1-naphthalenesulfonic acid metal salts, p-bromoaniline,S-amino-l-naphthalenesulfonic acid metal salts, p-chloroaniline,o-chloroaniline, 2, 4-dimethylaniline, m-toluidine, m-aminophenol,m-cholroaniline, p-arsanilic acid metal salts, p-aminophenylacetic acidmetal salts, o-aminobenzenesulfonic acid metal salts, 2-aminopyridine,2-amino-3-methylpyridine, 2-amino-4- methylpyridine,2-amino-S-methylpyridine, 2-amino-6- methylpyridine, phenylhydrazine,methyl hydrazine, symdimethyl hydrazine, unsym-dimethyl hydrazine,p-phenylenediamine, p,p'-methylenedianiline, 3,5-dimethylaniline,2-phenylethylamine, 8-amino-1-naphthol-5-sulfonic acid metal salts,6-amino-l-naphthol-S-sultonic acid metal salts, m-aminoacetophenone,o-aminobenzenethiol, 4,4-oxydianiline, 6-amino-m-toluenesulfonic acidmetal salts, p aminobenzonitrile, 2,5 dimethoxyaniline, 2-amino-4-phenylphenol and o-arsanilic acid metal salts.

Other nucleophilic reagents include amino acids and their soluble metalsalts, e.g., those of N-phenylglycine, glycine, DL-Z-aminohexanoic acid,L-()cystine, DL-aalanine, u-amino-iso-butyric acid, DL-a-amino-n-valericacid, DL-fi-phenylalanine, DL-a-aminophenylacetic acid,DL-Z-aminooctanoic acid, DL-aspartic acid, di-iso-leucine,L-(+)glutarnic acid, p-aminophenylacetic acid, DL-valine,DL-a-amino-n-butyric acid, DL-leucine, L- ()leucine, DL-methionine,4-aminobutyric acid, DL- serine and fl-alanine.

Still other such reagents include metal salts of hydroxylcontainingcompounds, e.g., the alcoholic and phenolic compounds such as4-hydroxybenzoic acid and its metal salts, 4-hydroxy, 4'-carboxybiphenyland its metal salts, CH OH(CHOH) CH OH, CH OI-I(CHOH) CH OH, l,3-dihydroxybenzene, 1,4-dihydroxybenzene, o-hydroxybenzaldehyde,4-hydroxybenzonitrile; metal salts of mercaptan compounds, whether alkylor aryl, e.g., o-car- HSCH CH CN, HSCH(CO H)CH CO H; selenoandtelluro-acids, e.g., HSeCH CO I-I, sulfinic acids RSO H, where R is a 1to 8 carbon alkyl group or an aryl group, e.g.,

Further reagents include hydrocarbonyl amines having a substituent ofthe group of PO H, AsO fiQO COSR, -CS R, CN, -CO PSO PO SO 0, -N=, -BOH, -SeO Of the many nucleophilic reagents characterized above which areoperable in this invention, it would be expected, as was indeed found,that the smaller molecules more readily penetrate and react more rapidlywith the lower and higher crosslinked vinylbenzylic sulfonium anionexchange resins, while the larger molecules of reagent more readilypenetrate and react more rapidly with the lower crosslinked sulfoniumresins. To determine the desirability and reaction characteristics of agiven sulfonium anion exchange resin with a given higher molecularweight nucleophilic reagent, a simple trial reaction followed by acapacity test is all that is needed. Alternatively, the absorptioncharacteristics of a sulfonium anion exchange resin for a givennucleophilic reagent can be tested by immersing a resin sample of thedesired crosslinkage in a large amount of solution of the desiredreagent, withdrawing the resin particles, draining the resin particlesfree of excess reagent, washing the reagent-wet resin with a solvent forthe nucleophile and determining the amount of reagent present in thewash solution. The amount of reagent absorbed by the resin is comparedwith the amount of reagent retained on the surface of glass beads orother impermeable particles having the same particle size as that of theresin particles. Such a comparison gives a value of relativepermeability of a given reagent for sulfonium resins of varyingcrosslinkages.

The reaction between a vinylbenzylic sulfonium anion exchange resin anda nucleophilic reagent is advantageously carried out at a reactiontemperature between 50 and C. for a reaction time of several hours up toabout 60 hours. If lower temperatures are employed, longer reactiontimes are generally desirable. Generally the nucleophilic reagent ispresent in excess up to.

about 200% of theory. The excess can be recovered, hence the amount ofexcess is not important. Alternatively, the exchange resin can be formedin situ from halomethyl-containing vinylaryl polymers and sulfides, asindicated and therein reacted with the indicated nucleophilic reagents.Thus, such a one-step method can be used instead of the two-step methodwherein sulfonium resin intermediate is first formed and then reactedwith a nucleophilic reagent, as indicated. The one-step method is shownin Example 7.

A method for preparing a vinylbenzylic sulfonium anion exchange resinreactant is as follows: A quantity of 100 grams of a chloromethylatedcopolymer containing in chemically combined form 2% by weightdivinylbenzene, a small amount of ethylvinylbenzene, the balancestyrene, 100 grams of dimethyl sulfide, 300 mls. of methylenedichloride, 300 mls, of methanol and 450 mls. of water were refluxed for33 hours with stirring under a hood. The product beads were filtered,washed alternately with water, methanol then with water again. Titrationwith silver nitrate showed that the capacity of the wet beads was 0.67milliequivalent (hereafter meq.) Cl /ml. Total weight of the wetfiltered product was 540 grams. The settled volume of 50 grams of thewet filtered product was 67 mls.

Examples which follow show ways in which the invention has beenpracticed. Typical reactions of'this invention can be summarized by thefollowing equation:

wherein R =vinylbenzylic resin matrix, B- =SO3', R-CC.O O

N Hz

or other nucleophile wherein n is an integer and SR R =sulfide, all aspreviously described in detail.

Example 1.-Reacti0n 0 s ulfonium resin with aqueous Na SO To 50 grams(67 mls. wet settled volume) of the filtered, washed sulfonium resindescribed above was added 25 grams of anhydrous sodium sulfite and 100mls. of water. The mixture was covered loosely and heated on a steambath under a hood for 40 hours and dimethyl sulfide was evolved. Theresulting resin was filtered, rinsed alternately with water andconcentrated hydrochloric acid, then given a final water rinse.Duplicate titrations with base showed the resin had a strong acidcontent of 0.68 meq./ml. A total of 57 mls, of wet settled cationexchange resin product was obtained. The basic resin structure was RCHSO H, wherein R represents the organic matrix.

Example 2.Reacti0n 0 sulfonium resin with aqueous NaSCH CO Na To 50grams (67 mls. wet settled volume) of the filtered, washed sulfoniumresin described above was added 33 grams of 95% thioglycolic acid, 100mls. of water and 21 grams of 98% sodium hydroxide. The flask containingthe mixture was covered loosely and the mixture was heated on a steambath under a hood for 40 hours. The resulting cation exchange resinproduct was filtered, rinsed alternately with water and withconcentrated hydrochloric acid, then given a final water rinse. Theresulting resin was filtered and weighed and amounted to 19 grams ofproduct. Its wet settled volume was 26 mls. This product was thentreated with excess sodium hydroxide solution, which caused it to swell.After Washing with several bed volumes of water, the resulting beads hada wet filtered Weight of 38.5 grams. Their wet settled volume was 52.5mls. This resin absorbed Cu++ strongly from an aqueous solution ofcopper sulfate, as indicated by a deep green color of the resin. Thecapacity for Cu++ was 0.67 meq/ml. By conversion to the hydrogen formand measuring weakly acidic 'ion exchange capacity, its SCH COONa+content was indicated to be 0.71 meq./ml. of bed.

Example 3.Reacti0n 0 sulfonium resin with aqueous NH CH CO Na To 50grams (67 mls. wet settled volume) of the filtered, washed sulfoniumresin described above was added 25 grams of glycine, 10 grams of 98%sodium hydroxide and 100 grams of water. The flask containing themixture was covered loosely and the mixture was heated on a steam bathunder a hood for 40 hours. The resulting resin was filtered, washed withammonium acetate solution, then with water. Weight of the wet filteredresin was 20 grams. Its wet settled volume was 25.5 mls. This resincontained a large number of glycine groups, as indicated by the factthat it absorbed Cu++ from an ammonium acetate buiTered solution ofcopper sulfate, turn ing a deep blue.

A glass tube 1.04 cms. in diameter was filled with this resin to form abed 25 cms. deep and having a volume of 20.5 mls. It was rinsed withexcess ammonium acetate solution, then with water. The resulting bed wasthen rinsed over a period of minutes with 25 mls. of 'a cobaltsulfate-nickel sulfate solution containing 0.52% Ni and 0.568% Co inapproximately l-normal ammonium acetate buffer. A green band wasobtained at the top of the column and a pink band at the bottom. Thecolor of the column was graduated in between top and bottom. The columnwas rinsed with approximately 50 mls. of water. Most of the pink bandwas eluted, leaving only a green color on the column, darkest at top,graduated to almost colorless at the bottom. Fractions 1 through 7 belowwere collected during these operations. The column was then washed withN-sulfuric acid, and fractions 8 and 9 were collected. The fractionsanalyzed as follows:

TABLE I v Percent by wt. nickel wt. cobalt (blank)- Dirty pink.

Colorless... Light pink.. Pink ..do.... Light pink.. Colorless...

Example 4.Reaction 0f sulfonium resin with various water-solublenucleophiles An anion exchange sulfonium resin made similarly to thepreceding description by reacting stoichiometric proportions of beads ofa chloromethylated crosslinked copolymer of 96 weight percent styreneand 4% divinylbenzene with dimethyl sulfide, containing 0.95 meq. of Cl/ml. wet settled volume, was used to make a series of ion exchange resinsas shown in Table II below. The reaction mixtures shown in Table II wereheated in lightly covered flasks for two days on a steam bath (exceptdiethylene triamine, 56 hours; ,B-mercaptoethane sulfonic acid, 32hours; and N-(hydroxyethyl)ethylenediaminetriacetic acid, 17 hours).

TABLE II.-REAGTANTS Resin Percent Cross- Sull'onium Water, Sodium N o.linking Resin, mls. Nucleophilc Grams Hydroxide,

grams grams 4 50 100 o-Aminobenzene sulionic acid 20 4.0 4 50 50 Taurine15 4. 4 50 50 N-(methyD-taurine. 15 4. 0 4 50 50 lsoleucine a a 15 4. 04 50 50 DL-phenylalanine 20 4. 0 4 50 50 DLalanine 12 4. 0 4 20 50Glutamic acid a a 20 9. 0 2 100 75 N-(methyl)-glaean1ine 30 2 100 150Iminodiacetic acid. 40 1 4O 2 50 150 Aspartic acid 20 l 20 2 50 75Methionine". 20 3. 0 2 100 60 Diethylene trial 48 0 2 100 200fl-mercaptoethane snllo 0 acid. 18 8 2 15 200N-(hydroxyethyl)ethylenediainine triacetic acid 8 1 KzCOa.

The resulting resins were filtered and washed alternately with water,acetone, water, N-sodium hydroxide and finally with water. They werethen vacuum filtered and weighed. A quantity of 100 mls. of N/ 10 coppersulfate solution was passed through a sample of about 2.0 mls. of eachresin. The resin samples were then rinsed with water and the Cu++ on theresins was eluted with 100 mls. of l-norrnal sulfuric acid. The coppersulfate was titrated iodometrically and the resin capacity wasdetermined. The resin samples, after the sodium hydroxide and waterwashes, were dried overnight in vacuo at 38 C. The following Table IIIsummarizes Cu++ absorption data of the resins just described.

TABLE III Final Final Wet Meq. Cu++ Percent Weight Resin No. Wt.,Settled AbSbd./llll. of Loss on Drying g. VOL, mls. Wet Settled (H OCon- Resin tent) 31 38 0. 83 25 31 40 O. 78 38 33 42 0. 60 39 30 39 0.2.2 30 38 0. 26 27 35 0. 30 36 30 38 (J. 52 40 72 90 0. (i0 37 83 9S 1.04 10 0. 40 13 19 0. 07 36 55 0. 55 32 42 1 0. 82 G5 80 0. 59

1 11+ capacity, resin in 11+ l0l'll1.

Example 5.Reacti0n of sulfonium resin with aqueous trz'soa'iummercaptosuccinate A mixture of 100 grams (wet filtered weight) of a 2%crosslinked sulfonium resin, prepared as previously described, 50 gramsof mercaptosuccinic acid, 35 grams of 98% sodium hydroxide pellets and300 mls. of water were heated on a steam bath under a hood for 48 hoursin a flask provided with a reflux condenser and a stirrer. The cationexchange resin beads so obtained were filtered, washed with several bedvolumes of water and weighed. Their wet filtered weight was 99 grams.The resulting wet resin was rinsed with 8-normal hydrochloric acid,whereupon it shrank approximately 30%. After washing alternately withseveral bed volumes of 10% sodium hydroxide and water, the wet filteredresin weight was again 99 grams. The wet settled volume of the resultingresin beads was 133 mls. It had a Cu++ capacity of 0.91 meq./ml.

Example 6.Reaclion of sulfonium resin with aqueous disodiumiminodiacetate A mixture of 50 grams (wet filtered weight) of a 2%crosslinked sulfonium resin, prepared as previously indicated, grams ofiminodiacetic acid, 20 grams of anhydrous potassium carbonate and 150mls. of water was heated on a steam bath under a hood for 56 hourswithout agitation. The resulting resin was filtered and rinsed withseveral bed volumes of water. Its wet settled volume was then 37.5 mls.while its wet filtered weight was 27 grams. It had a Cu capacity of 0.83meq./ml.

Example 7.In situ reaction (one-step method) A quantity of 50 grams ofbeads of a chloromethylated crosslinked copolymer of a preponderance ofstyrene, a small amount of ethylvinylbenzene and 4% divinylbenzene(50-100 mesh, 16.2% C1), grams of mercaptosuccinic acid, 85 grams ofsodium hydroxide pellets, grams of toluene, mls. of dioxane, 250 mls. ofwater and 100 mls. of dimethyl sulfide was mixed together in atwo-liter, three-necked flask equipped with a stirrer and an eflicientreflux condenser. The mixture was heated at reflux (62 C.) for 21 hours.The product resin was filtered and washed well with water, methanol, andagain with water. Final volume of wet resin product was 168 mls. The wetproduct had a capacity for Cu of 1.56 meq./ml. (0.73 gram atomsCu++/liter).

Example 8.Reaction in presence of a polar solvent A quantity of 100grains of wet filtered water-swollen sulfonium resin (about 134 mls. wetsettled volume, capacity 0.84 meq. Cl/ml.), prepared as above-indicatedand contained in a filter tunnel, was rinsed well and dehydrated withabout two liters of commercial grade methanol. The sulfonium resin, 300mls. of methanol, and 50 mls. of anhydrous dimethylethanolamine (97%)were stirred at reflux for 24 hours. The anion exchange resin productwas filtered and washed well with water, methanol, N-hydrochloric acidand again with water. The final wet settled volume of the resin productwas 127 mls. The resin had a wet settled Clcapacity of 0.80 meq./ml. Asample of the product resin was dried on a moisture balance and had aweight loss of 67.7%. Its nitrogen content was 4.66%.

Example 9.-Reacti0n after removal of solvent A quantity of 13 mls. ofsulfonium resin (from chloromethylated 2% crosslinked polystyrene beads,50-100 mesh) which had a wet settled volume capacity of 0.84 meq.Cl/ml., was placed in a small column and rinsed with one liter of NNa SOThe resin was then rinsed with water, 500 mls. of methanol, 500 mls. ofacetone, 500 mls. of ether, and air dried a few minutes. The beadscontaining chemically absorbed sulfite were heated at about 95 C. in acontainer protected with a drying tube for about 16 hours. The productbeads then were heated With 8 NHC1 (sufficient to slurry the mixture)for about 16 hours. The beads were then rinsed extensively with water.They had a wet volume of 5 mls. and a strong acid cation exchangecapacity of 0.21 meq./ml.

Example 10.Highl v cross-linked bead cation exchanger A quantity of 5.0mls. of sulfonium resin prepared from 16% divinylbenzene-crosslinkedchloromethylstyrene and the use of one liter of 0.05 NNa CO solution.

dimethyl sulfide, having 1.74 meq. Cl-/ ml. of wet settled resin, 5.0grams of Na SO and 50 mls. of water was heated on a steam bath for 24hours. The filtered resin was rinsed with water, 4 NHCl, and again withwater. The wet settled volume of the beads was 4.2 mls. The beads had0.36 meq./ ml. of strongly acid cation exchange capacity.

Example 1].Preparati0n of cation exchange resins from sulfonium sulfateand carbonate resins Approximately 20 mls. of 4% crosslinked sulfoniumresin, 1.06 meq. Cl"/ml., was placed in a column and converted to thesulfate form by rinsing with one liter of 0.05 'N+Na S O The resin wasthen rinsed well with water, and had a volume of 22 mls. and a residualionic chloride content of less than 0.002 meq./ ml. of wet settledvolume.

The sulfonium sulfate resin (15 mls.) was heated overnight on a steambath with 5.0 mls. of water and 43 grams of a 25% solution of disodiumiminodiacetate.

Example 14.-Cmparalive reactions of different sulfonium resins Sulfoniumanion exchange resins prepared by reacting 2%crosslinked-chloromethylated polystyrene with methyl hydroxyethylsulfide (I), diethyl sulfide (II) and dimethyl sulfide (III) werereacted with trisodium mercaptosuccinate and compared as to properties.Comparative preparations and properties are summarized in the followingThe re- 20 table.

TABLE IV Reaction Conditions Properties of Product Wt. SulfoniurnProduct Unit Structure Wet Wet Volume Resin(wet Wt. Rcactant Solvent,etc. Settled Capacity,

filtered) Volume, meq. Cu/ml.

mls.

I. 94 g. (9.9 mls.) 5.0 g. mercaptosuccinic acid. 3.5g. NaOH pelletsplus 150 R-C}I2SCH OOONa 9. 9 0.71

' mls. H O. Refiuxed for 47 hours. CI-I COONa II. 10.3 g. (10.3 mls.) dod0 BCII2-SOH COONa 9. 5 0.95

- C11 0 0 ON a III 100 g. (13411115.).-. 50 g. mcrcaptosuccinic acid 35g. NaOI-I pellets plus 300 R=CH CI-IC H4 133 0. l9

7 mls. H O. Heated on steam bath 48 hours.

sulting anion exchange resin was filtered and rinsed well with water,methanol, and again with water. A 5.0 ml. sample of the resin was rinsedwith 200 mls. of N/ 10 CuSO, solution and then with water. The resinabsorbed 1.10 meq. of Cu++/ ml. of wet settled volume. The total volumeof product resin was 12.5 mls.

The preceding procedure was repeated, except that the original resin wasconverted to the carbonate form by The bed volume of resin in thecarbonate form was 24 mls. Its residual chloride was less than 0.003meq./ml. The final resin after reaction of the above with iminodiacetatesolution had a wet settled volume of 11.2 mls. and a Cu++ capacity of1.12 meq./ml.

Example ]2.Resin preparation with water-insoluble solvents A quantity ofgrams (approximately 26 mls.) of 2% crosslinked sulfonium resin beads,0.84 meq. Cl /ml., was washed with water and filtered. Then 50 mls. oftoluene and 10 mls. of 97% Me- NCH CH OH were added. The mixture washeated on a steam bath overnight in a capped bottle. The resulting anionexchange resin was filtered, washed with dilute HCl, and then withwater. The wet resin had a capacity of 0.74 meq. Cl /ml. of

bed (total bed volume was 18 mls.). The Wet resin was dried (weight losswas 69%) and analyzed for nitrogen. Its nitrogen content was 4.66%.

The preceding procedure was repeated, except that 20 grams of beadswhich contained only methanol as swelling agent, equivalent to 27.5grams of water-swollen beads, was used. Final volume of product was 30mls. Its chloride capacity was 0.78 meq./ml. Weight loss on drying theproduct was 67%. Nitrogen content of dried product was 4.53%.

Example ]5.-Reaction of sulfonium resin made from tetramethylene sulfidewith Na SO A quantity of 5 .0 mls., wet settled volume, of 1%crosslinked sulfonium resin beads, having a wet volume capacity of 0.41meq. Cl-/ml., prepared by reacting a polymeric chloromethylstyrene withtetramethylene sulfide to the extent of 50%, was heated on a steam bathto C. with 50 mls. of water and 2.0 grams of Na SO for 18 hours. Thevolume of the resulting product after washing with water, then withl2-norrnal hydrochloric acid, then with water, was 9.2 mls. A total of3.3 meq. of exchangeable H+ ions was present in the water washedproduct, or 0.36 meq. H /ml. The sulfonium chloride groups had reactedto form SO Na+ groups. Since the final product contained a total of 3.3meq. of exchangeable H+ and the starting material, a 5/ 15.5 aliquot ofa 12.3 meq. total Clresin, yields a theoretical total of 4.0 meq. H+,based on Cl content of the starting chloromethylated resin beads, theprecent conversion of sulfonurn chloride to SO Na was 3.3 /4.0 or about82 0.

Example 16.Reacti0n with iminodiacetonitrile A quantity of 27 grams ofvinylbenzyl dimethylsulfoniurn chloride resin, 1% DVB crosslinked, 50100U.S. mesh size, methanol wet capacity 0.94 meq./wet gram, 7.0 gramsHN(CH CN) 22 grams methanol, 54 grams ethylene glycol, 20 grams C H OCHCH OCH CH OH was mixed and heated on a steam bath for 64 hours. Resinproduct was filtered and washed successively with water, acetone andwater. Weight of filtered resin product was 9 grams of dark brownproduct. Its percent moisture was 38. After centrifuging the product,its moisture content was 22%. A dry sample of resin had a nitrogenanalysis of 7.71:0.l0% N.

A quantity of 2.0 grams of the wet filtered product resin was heated 4days on a steam bath with aqueous 9 molar HBr. Product resin was darkbrown. Its volume was 2.6 mls. (wet settled). Its capacity for Cu++ fromammoniacal solution was 0.34/2.6=O.13 meq./ ml. This indicated thatGHzCOOH OHtOOOH groups were formed on hydrolysis.

Example l7.-Reactin with ammonia A quantity of 100 mls. of commercialconcentrated aqueous ammonia and 40 grams of the sulfonium resin ofExample 16 (CH OH wet, filtered) was heated together on a steam bath for64 hours. Yield was 11.5 grams (17 mls. wet settled volume in water) ofa light tan resin. That it possessed vinylbenzylamine groupings wasproved by the fact that the resin turned light green when washed withaqueous CuSO solution, then with water. The product resin, which hadbeen rinsed successively with water, acetone and water, had a watercontent (loss on drying) of 39.6%. The centrifuged resin product had awater content of 38.3%. A dried sample gave a nitrogen analysis of2.932009%.

Example 18.Reacti0n with sodium thiosulfate To 2 0 grams of the CH OHswollen resin of Example 16 was added 15 grams of solid Na S O Themixture was heated with 100 mls. of HOCH CH OH on a steam bath for 64hours. Final resin, washed successively with water, acetone and water,then filtered, weighed 24 grams. It turned dark blue in ammoniacal CuSOsolution. Water content of the wet vacuum filtered resin was 76% aftercentrifugation. Its copper capacity, aqueous dilute CuSO was 0.47meq./ml.

In an analogous experiment, using water only as solvent in reacting thesulfonium resin and the Na S O a resin was obtained having very similarproperties and having 0.51 meq. Cu++ capacity per ml. of Na+ form ofresin. The product resin was found to be convertible with a hydrochloricacid wash to a resin having 0.46 meq. strongly acidic capacity per ml.of Na+ form resin converted. This indicates that the resin was polymericvinylbenzyl thiosulfate, Na+ form.

Example 19.-Reaczi0n with p-sulfanilamide To 16 grams of p-sulfanilamidein 23 grams of ethylene glycol plus 16 grams of monoethyl ether ofethylene glycol was added 16 grams of methanol-wet filtered vinylbenzyldimethylsulfonium chloride resin, crosslinked with 1% DVB. This mixturewas heated on a steam bath for 64 hours under a hood. The product resinwas washed successively with water, acetone and water and vacuumfiltered. Weight of product resin Was 7 grams. Its water content was25.1%. The centrifuged product contained 21.8% water. The dry resin wasfound to have 6.131003% N.

Example 20.Reacti0n with p-aminoacetophenone To grams ofp-aminoacetophenone in 30 grams ethylene glycol was added 15 grams offiltered CH OH swollen 1% DVB crosslinked vinylbenzyl dimethylsulfoniumchloride anion exchange resin. The mixture was heated for 64 hours on asteam bath. Filtered resin product was washed successively with water,acetone and water. It weighed 4 grams and had a water content of 16.8%.The centrifuged resin product had a water content of 13.1%. Its percentN, dry resin basis, was 4.04:0.05%.

Example 21.Reacti0n with hydrazine plus dimethylethanolamine To 150 mls.of 1% DVB crosslinked, 50-100 mesh polymeric vinylbenzyldimethylsulfonium chloride resin temperature, was 3.5%.

( meq./ml.) was added sufficient water to fill the resin voids (ca. 65mls.) plus 10 mls. (total of 75 mls. water added to wet the resin). Then109 meq. (5.5 grams) of hydrazine (prac., aq. 64% solution) and 32 meq.(2.75 grams) of pure dimethylethanolamine were added. The mixture washeated on the steam bath for 62 hours. The filtered product beads wererinsed successively with water, with two liters of aqueous 3-normalNaOH, and with water. Volume of wet resin product was 60 mls. A sample(2.3 mls.) was eluted with 400 mls. of 4% NaCl. Found NaOH in eluate was0.45 meq. Then a 30 mls. sample of the resin, OH form, was placed in anexcess of 0.100-normal hydrochloric acid, and the resin was filtered offafter 2 days. Found consumption of HCl was 0.60 meq. Thus, the strongbase capacity of the resin, due to dimethylethanolimino groups, was 0.2meq./ml., and the weak base capacity, due to hydrazine groups, was 0.3meq./ml.

Example 22.Reacti0n with diethyl malonate A quantity of 255 mls. of 2%DVB crosslinked polymeric vinylbenzyl dimethylsulfonium chloride resinbeads, 50-100 U.S. mesh, 0.84 meq./ml., was rinsed with three liters ofcommercial methanol and allowed to stand in methanol for one day. Tosuch beads and methanol (total volume 400 mls.) was added 110 grams ofdiethyl malonate and 20 grams of commercial sodium methylate. Themixture became warm and was heated at reflux with stirring for 64 hours.The resulting product beads were washed with methanol then with water,to give a wetfiltered weight of 156 grams.

The resulting water-wet beads, 70 grams of NaOH pellets, 200 mls. ofwater and mls. of diethylene glycol were heated together on a steam bathfor 18 hours. The product beads were filtered and washed successivelywith water, methanol and water. Their wet filtered weight was 151 grams.A portion thereof was analyzed and found to have a Cu++ capacity of 1.24meq./ml., indicating that most of the ester groups had been hydrolyzedto carboxyl groups. It was necessary to continue the hydrolysis of thebeads in the water-ethylene glycol-NaOH mixture for an additional 42hours in order to hydrolyze substantially all of the ester groups. Theproduct, containing methenyl dicarboxylate groups attached throughmethenyl carbon atoms to benzylic carbon atoms of the polymer had a Cu++capacity of 1.40 meq./ml.

The following examples are presented to demonstrate the reactivity ofrepresentative ionizable nucleophilic reagents with benzyl chlorideunder conditions as specified above to characterize those reagents whichare operable in the process of this invention.

Example 23.Reaction of benzyl chloride with ammonia To 0.25 ml., 2.18meq., of benzyl chloride (hereafter BzCl) in 25 mls. of stock solution(65% ethanol, 35% water) was added 1.60 mls. 15-normal aqueous ammonia.The mixture was reacted at room temperature in a capped, mechanicallyshaken bottle for 17.5 hours. Then 25 mls. of stock solution and excesssulfuric acid were added to the sample, and it was titratedpotentiometrically for chloride ion. Found: percent reaction was 9.6.Found: percent reaction on a blank, wherein 0.25 ml. BzCl and 25 mls.stock solution were shaken for 17.5 hours at room Net reaction of BzClwith NH thus was 6.1% of theory for complete reaction.

Example 24.Reacti0n of benzyl chloride with dimethylethanolamine Theprocedure of Example 22 was repeated with 0.300 gram Me NCH CH OH, 3.37meq., in place of ammonia. Found: net reaction of Me NCH CI-I OH withBzCl to liberate Cl was 94.5% of theoretical.

ExampIe-25.Reactin 0] benzyl chloride with isoleucine The procedure ofExample 22 was repeated with 0.300 gram of isoleucine, 2.29 meq., inplace of ammonia. Found: net reaction was 51% of theoretical.

Example 26.-Reacti0n 0 benzyl chloride with iminodiacetic acid disodiumsalt The procedure of Example 22 was repeated with 0.300 gram NH(CHCOOH) 2.27 meq. plus 1.14 mls. 2-normal NaOH, 2.28 meq. in place ofammonia. Found: net reaction was 8.4%.

Example 27.Reacti0n 0 benzyl chloride with p-aminoacetopheno te Theprocedure of Example 22 was repeated with 0.300 gram.p-aminoacetophenone, 2.22 meq., in place of ammonia. Found: net reactionwas 13%.

Example 28.-Reacti0n of benzyl chloride with sodium sulfite Theprocedure of Example 22 was repeated with 0.300 gram Na SO in place ofammonia. Found: net reaction was 14.8%.

What claimed is:

1. A method for making an exchange resin by reacting in substantiallystoichiometric proportions at a reaction temperature of 50-100 C. avinylbenzylic sulfonium anion exchange resin with an ionizablenucleophilic reagent of the group consisting of those which have one ormore exchanging moieties and those which have one or more ester, amide,nitrile or alkanol moieties which can be converted to exchangingmoieties by hydrolysis or oxidation reactions, respectively, and issoluble to the extent of at least 5% by weight in a member of the groupconsisting of water and aliphatic liquid alcohols having from lto carbonatoms in the-molecule, said reagent being one having a property ofreacting in stoichiometric proportions with benzyl chloride at to 100 C.to displace at least 5 mole percent of chloride therefrom in 48 hours,which reagent comprises-a group which reacts to establish a covalentbond with the benzylic carbon atom of the resin and to yield a sulfideby-product, to give a substituted vinylbenzylic resin of the groupconsisting of those which possess exchanging moieties and those whichhave one or more ester, amide, nitrile or alkanol groups which can beconverted to have exchanging moieties by hydrolysis or oxidationreactions.

2. The method of claim 1 wherein the nucleophilic reagent is an aminoacid salt.

3. The method of claim 1 wherein the nucleophilic reagent is an amine.

4. The method of claim 1 wherein the nucleophilic reagent'is amercaptocarboxylic acid.

5. The method of claim 1 wherein the nucleophilic reagent is an alkalimetal salt of a dialkyl ester of malonic acid.

6. The method of claim 1 wherein the nucleophilic reagent is sodiumsulfite.

7. The method of claim 1 wherein the nucleophilic reagent is sodiumthioglycolate.

8. The method of claim 1 wherein the nucleophilic reagent is sodiumglycinate.

9. The method of claim 1 wherein the nucleophilic reagent is trisodi-ulmmercaptosuccinate.

10. The method of claim 1 wherein the nucleophilic reagent is disodiumiminodiacetate.

11. The method of claim 1 wherein the nucleophilic reagent is dimethylethanolamine.

12. The method of claim 1 wherein the nucleophilic reagent is diethylenetriamine.

13. The method of claim 1 wherein the nucleophilic reagent is N(methyl)-glucamine.

14. The method of claim 1 wherein the reaction medium is a polar solventfor the reagent.

15. The method of claim 1 wherein the reaction medium is water.

16. The method of claim 1 wherein the po1y(vinylbenzylic sulfonium)anion exchange resin is formed in situ from apoly(halomet-hyl-containing vinylaryl) compound and a sulfide having theformula R R S wherein R and R individually represent a member of thegroup consisting of 1 to 4 carbon alkyl radicals and 2 to 4 carbonhydroxyalkyl radicals and together represent polymethylene groups and lto 4 carbon alkyl-substit-uted polymethylene groups having a total of 4to 12 carbon atoms.

17. A polymeric vinylbenzylic ion exchange resin, the matrix of whichhas a preponderance of combined vinylbenzylic groups crosslinked with0.2-20 weight percent of a dialkenyl crosslinking agent, having, asexchanging groups covalently attached to benzylic carbon atoms, a memberof the group consisting of thiosulfate groups, attached throughoxygen-free sulfur atoms; methenyl dicarboxylate groups, attachedthrough methenyl carbon atoms; and iminoacetophenone groups, attachedthrough imino nitrogen atoms.

18. A polymeric vinylbenzylic thiosulfate ion exchange resin, the matrixof which has a preponderance of combined vinylbenzylic groupscrosslinked with 0.2-20 weight percent of a dialkenyl crosslinkingagent, having thiosulfate exchanging groups covalently attached throughoxygen-free sulfur atoms to benzylic carbon atoms.

19. A polymeric vinylbenzylic methenyl dicarboxylate ion exchange resin,the matrix of which has a preponderance of combined vinylbenzylic groupscrosslinked with 0.220 weight percent of a dialkenyl crosslinking agent,having methenyl dicarboxylate groups covalently attached throughmethenyl carbon atoms to benzylic carbon atoms.

20. A polymeric vinylbenzylic iminoacetophenone ion exchange resin, thematrix of which has a preponderance of combined vinylbenzylic groupscrosslinked with 0.2-20 weight percent of a dialkenyl crosslinkingagent, having iminoacetophenone groups covalently attached through iminonitrogen atoms to benzylic carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,713,038 7/1955De Jong 2602.l 2,768,990 10/1956 De Jong 2602.1 2,895,925 7/1959 Hwa 2602.1 3,013,994 12/1961 Hatch 2602.l

OTHER REFERENCES Toennies et al.: J.A.C.S., vol. 67, pp. 11414, July1945.

WILLIAM H. SHORT, Primary Examiner.

HAROLD N. BURSTEIN, J. C. MARTIN, C. A.

WENDEL, Assistant Examiners.

1. A METHOD FOR MAKING AN EXCHANGE RESIN BY REACTING IN SUBSTANTIALLYSTOCHIOMETRIC PROPORTIONS AT A REACTION TEMPERATURE OF 50*-100*C. AVINYLBENZYLIC SULFONIUM ANION EXCHANGE RESIN WITH AN IONIZABLENUCLEOPHILIC REAGENT OF THE GROUP CONSISTING OF THOSE WHICH HAVE ONE ORMORE EXCHANGING MOIETIES AND THOSE WHICH HAVE ONE OR MORE ESTER, AMIDE,NITRILE OR ALKANOL MOIETIES WHICH CAN BE CONVERTED TO EXCHANGINGMOIETIES BY HYDROLYSIS OR OXIDATION REACTIONS, RESPECTIVELY, AND ISSOLUBLE TO THE CONSISTING OF WATER AND ALIPHATIC LIQUID ALCOHOLS HAVINGFROM 1 TO 10 CARBON ATOMS IN THE MOLECULE, SAID REAGENT BEING ONE HAVINGA PROPERTY OF REACTING IN STOICHIOMETRIC PROPORTIONS WITH BENZYLCHLORIDE AT 20* TO 100*C. TO DISPLACE AT LEAST 5 MOLE PERCENT OFCHLORIDE THEREFROM IN 48 HOURS, WHICH REAGENT COMPRISES A GROUP WHICHREACTS TO ESTABLISH A COVALENT BOND WITH THE BENZYLIC CARBON ATOM OF THERESIN AND TO YIELD A SULFIDE BY-PRODUCT, TO GIVE A SUBSTITUTEDVINYLBENZYLIC RESIN OF THE GROUP CONSISTING OF THOSE WHICH POSSESSEXCHANGING MOIETIES AND THOSE WHICH HAVE ONE OR MORE ESTER, AMIDE,NITRILE OR ALKANOL GROUPS WHICH CAN BE CONVERTED TO HAVE EXCHANGINGMOIETIES BY HYDROLYSIS OR OXIDATION REACTIONS.